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CN110877427B - 一种含有空心陶瓷球的复合材料及其制备方法 - Google Patents

一种含有空心陶瓷球的复合材料及其制备方法 Download PDF

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CN110877427B
CN110877427B CN201910841136.8A CN201910841136A CN110877427B CN 110877427 B CN110877427 B CN 110877427B CN 201910841136 A CN201910841136 A CN 201910841136A CN 110877427 B CN110877427 B CN 110877427B
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hollow ceramic
composite
layer
powder
metal
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CN110877427A (zh
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牛春明
李美平
何启平
李俊
姜璠
李智辉
季欣
孟照海
龚顺祥
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Xian Jiaotong University
CNPC Chuanqing Drilling Engineering Co Ltd
Changqing Downhole Operation Co of CNPC Chuanqing Drilling Engineering Co Ltd
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Xian Jiaotong University
CNPC Chuanqing Drilling Engineering Co Ltd
Changqing Downhole Operation Co of CNPC Chuanqing Drilling Engineering Co Ltd
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Abstract

一种含有空心陶瓷球的复合材料及其制备方法。包括通过3D打印方法制备的一种含有空心陶瓷球复合物的耐冲击梯度复合物部件，以及共混融合方式获得的空心陶瓷球‑聚合物复合物介电材料。本发明的优点在于所得的复合材料具有相对低密度，高强度的特点。耐冲击梯度复合物部件为层状复合物，在与层垂直的方向，复合物的组成和性能可以根据设计进行调节，比如通过调控组成变化，使复合物的机械性能由软过度到硬，呈梯度变化，同时根据需要准确控制性能不同层间的厚度。空心陶瓷球‑高聚物复合物介电材料的介电性能、导热性能和机械性能具有较大的增加。

Description

一种含有空心陶瓷球的复合材料及其制备方法
技术领域
本发明属于复合材料制备技术领域，尤其是涉及一种含有空心陶瓷球的复合材料及其制备方法。
背景技术
空心陶瓷球是一种可以大规模制备的新型材料，目前主要用作支撑剂，用于石油和天然气开采。空心陶瓷球具有密度低和强度高的特点，在开发新型复合物方向，具有很大的应用潜力。在环氧树脂等有机电介质材料中添加，可以提高这些有机物的导热系数、介电性能以及机械强度。在金属材料中添加，可以有效改进金属材料的机械性能，制备低密度、高强度、耐冲击的复合材料，这种材料作为结构材料在许多领域有重要的应用。在用作保护材料时同其他材料结合，形成梯度层状结构，可以进一步提高性能。比如表面层为高硬度金属材料，中间层为复合物，底层为高聚物软材料，可以极大提高材料的耐冲击力。3D打印是一种快速成型技术，采用逐层打印的方式来构造物件，通过对层状结构的组成和结构参数调控，可以对材料的性能进行精确设计和控制。
发明内容
有鉴于此，本发明旨在利用空心陶瓷球的低密度和高强度的特点，改进高聚物和金属材料的性能，制备新型复合物材料，进一步提出一种含有空心陶瓷球的复合材料及其制备方法，以克服现有技术的不足。
本发明的一个方面是提供一种含有空心陶瓷球复合物的耐冲击梯度复合物部件的3D打印方法，包括如下步骤：
1）设计部件的尺寸和形状以及内部的层状结构；
2）提供两种原材料，一种是金属或高聚物粉末，另一种是空心陶瓷球；
3）根据设计提供一定厚度的金属或高聚物粉末，然后用热源将粉末融熔和固化，形成金属层或高聚物层，根据设计重复打印金属层或高聚物层直到达到设计的金属层或高聚物层厚度；
4）在金属或高聚物表面提供一层空心陶瓷球，提供金属或高聚物粉末直到所有球之间的空隙被填满，然后用热源将粉末融熔和固化，形成金属或高聚物-陶瓷球复合物层，重复打印复合物层直到达到设计的厚度；
5）重复步骤3）和4）形成耐冲击梯度复合物部件。
本发明的另一个方面是提供一种含有空心陶瓷球复合物的耐冲击梯度复合物部件的3D打印方法，其特征在于，包括如下步骤：
1）设计部件的尺寸和形状以及内部的层状结构；
2）提供原材料，所述原材料含有高聚物、固化剂和空心陶瓷球；
3）根据设计提供一定厚度的原材料，然后用热源固化，形成含有空心陶瓷球的高聚物层，根据设计重复打印直到达到设计的厚度，形成耐冲击梯度复合物部件。
本发明的另一个方面是提供一种空心陶瓷球-高聚物复合物介电材料的制备方法，所述材料制备方法包括如下步骤：
1）提供一种空心陶瓷球和一种高聚物材料；
2）将所述高聚物材料与固化剂、增塑剂混合均匀；
3）加入空心陶瓷球，搅拌混合均匀，真空脱气；
4）加热步骤3所得混合物，进行固化处理，得到空心陶瓷球-高聚物复合物介电材料。
本发明的优点在于所得的复合材料具有相对低密度，高强度的特点。耐冲击梯度复合物部件为层状复合物，在与层垂直的方向，复合物的组成和性能可以根据设计进行调节，比如通过调控组成变化，使复合物的机械性能由软过度到硬，呈梯度变化，同时根据需要准确控制性能不同层间的厚度。空心陶瓷球-高聚物复合物介电材料的介电性能、导热性能和机械性能具有较大的增加。
附图说明
图1为本发明的3D打印示意图；
图2为本发明所用的高强度空心陶瓷球；
图3为本发明所用的空心陶瓷球横截面电子显微镜图；
图4为本发明所制备的环氧树脂-空心球复合物的光学显微镜图；
图5为本发明所用的均匀空心陶瓷球球复合物；
图6为本发明制备的梯度复合物部件的一个示意图；
图7为本发明制备的梯度复合物部件的另一个实例示意图。
其中：1-3D打印原料，2-刮刀，3-激光，4-梯度复合物，5-收集器，6-空心陶瓷球，7-基体，8-纯基体，9-复合物，10-薄层纯基体，11-薄层复合物
具体实施方式
下面结合具体实施方式来对本发明作进一步的说明，使其技术内容更加清楚和便于理解。本发明可以通过许多不同形式的实施例来得以体现，本发明的保护范围并非仅限于文中提到的实施例。
本发明的一个方面是提供一种含有空心陶瓷球复合物的耐冲击梯度复合物部件的3D打印方法，包括如下步骤：
1）设计部件的尺寸和形状以及内部的层状结构；
2）提供两种原材料，一种是金属粉末，另一种是空心陶瓷球；
3）根据设计提供一定厚度的金属粉末，然后用热源将粉末融熔和固化，形成金属层，根据设计重复打印金属层直到达到设计的金属层厚度；
4）在金属层表面提供一层空心陶瓷球，提供金属粉末直到所有球之间的空隙被填满，然后用热源将粉末融熔和固化，形成金属-陶瓷球复合物层，重复打印复合物层直到达到设计的厚度；
5）重复步骤3）和4）形成耐冲击梯度复合物部件。
优选的，所述步骤3）和步骤4）所述的熔融温度的选择并无特别要求，选择相应材料的常规熔融温度即可。
优选的，所述金属粉末包括但不限于铝粉和钛粉。
本发明的另一个方面是提供一种含有空心陶瓷球复合物的耐冲击梯度复合物部件的3D打印方法，其特征在于，包括如下步骤：
1）设计部件的尺寸和形状以及内部的层状结构；
2）提供原材料，所述原材料含有高聚物、固化剂和空心陶瓷球；
3）根据设计提供一定厚度的原材料，然后用热源固化，形成含有空心陶瓷球的高聚物层，根据设计重复打印直到达到设计的厚度，形成耐冲击梯度复合物部件。
优选的，高聚物粉末包括：环氧树脂与偶联剂混合物，环氧树脂，Nylon，聚醚醚酮（PEEK），聚苯硫醚（PPS），聚酰亚胺（PI）。
优选的，所述环氧树脂与偶联剂的混合物中，所述偶联剂可选择本领域内常见的偶联剂，例如多元羧酸和环酐。
优选的，所述空心陶瓷球的直径为50微米-5毫米，空心陶瓷球壁厚同球半径的比例为1/3–2/3。
优选的，所述空心陶瓷球的破碎率在35MPa下小于5，在60MPa下小于5，在压强高于86MPa时小于5。
优选的，所述空心陶瓷球的材料包括但不限于：玻璃，SiO2，刚玉（Al2O3），莫来石，刚玉和玻璃体的混合物。
本发明的另一个方面是提供一种含有空心陶瓷球复合物的耐冲击梯度复合物部件，使用前述3D打印方法制备。
本发明的另一个方面是提供一种空心陶瓷球-高聚物复合物介电材料的制备方法，所述材料制备方法包括如下步骤：
1）提供一种空心陶瓷球和一种高聚物材料；
2）将所述高聚物材料与固化剂、增塑剂混合均匀；
3）加入空心陶瓷球，搅拌混合均匀，真空脱气；
4）加热步骤3所得混合物，进行固化处理，得到空心陶瓷球-高聚物复合物介电材料。
优选的，所述固化剂和增塑剂为本领域内常规的固化剂和增塑剂。
优选的，所述加热固化并无特别要求，满足相应高聚物材料的固化条件即可。
优选的，所述空心陶瓷球的直径为50微米-5毫米，空心陶瓷球壁厚同球半径的比例为1/3–2/3。
优选的，所述空心陶瓷球的材料包括但不限于：玻璃，SiO2，刚玉（Al2O3），莫来石，刚玉和玻璃体的混合物；所述高聚物包括环氧树脂，Nylon，聚醚醚酮（PEEK），聚苯硫醚（PPS），聚酰亚胺（PI）以及这些材料的混合物。
本发明的另一个方面是提供一种空心陶瓷球-高聚物复合物介电材料，所述材料使用前述方法制备。
实施例1：空心陶瓷球-环氧树脂梯度复合物
将双酚A环氧树脂（Bisphenol-A epoxy resin，DGEBA），聚己内酯二元醇和三芳基六氟锑酸锍鎓盐阳离子光引发剂按一定比例混合制备成液体A；在液体A中添加一定比例的空心陶瓷球制备B。
如图1所示，提供一定厚度的B，紫外光照射一定时间使环氧树脂固化形成复合物薄层，重复以上步骤直到复合物层的厚度达到设计厚度，然后提供一定厚度的A，紫外光照射一定时间使环氧树脂固化形成纯环氧树脂薄层，重复打印纯环氧树脂直到纯环氧树脂层达到设计厚度。重复打印复合物层和纯环氧树脂层直到形成设计的梯度复合物产物，在真空下150℃加热产物进一步使环氧树脂固化并去除产物中的应力。
实施例2：空心陶瓷球-钛梯度复合物
如图1所示，提供一定厚度的空心陶瓷球（至少一个单层），在陶瓷球上提供一个薄层钛粉，通过震动或其它机制使钛粉完全将陶瓷球间的空隙填充，然后用激光照射一定时间使钛粉凝聚将空心球连接成一体，形成空心陶瓷球-钛复合物薄层，重复以上步骤直到复合物层的厚度达到设计厚度，然后提供一定厚度的钛粉，用激光照射一定时间使钛粉凝聚形成纯钛薄层，重复打印纯钛直到纯钛层达到设计厚度。重复打印复合物层和纯钛层直到形成设计的梯度复合物产物，在真空下高温处理进一步使凝聚固化并去除产物中的应力。
实施例3：空心陶瓷球-环氧树脂复合物复合物
将双酚A环氧树脂（Bisphenol-A epoxy resin，DGEBA），固化剂甲基四氢苯酐（Methyl Tetrahydrophthalic Anhydride ，MTHPA)和增速剂N,N-二甲基苄胺（N,N-dimethylbenzylamine，BDMA)按100:86:2的比例混合，添加65%重量百分比的空心陶瓷球（圆度＞0.95，视密度～2.7，86MPa压强下的破碎率＜5%）,搅拌均匀后，在60℃真空下脱气30分钟，然后在100℃固化2小时，150℃固化10小时获得空心陶瓷球-环氧树脂复合物。
在光学显微镜下，如图4所示，空心陶瓷球接近紧密堆积，紧密堆积间的空隙由环氧树脂填充，将空心陶瓷球紧密连接在一起形成复合物。图5显示空心陶瓷球在基体中均匀分布。
如表1所示，相比在同样条件下制备的纯环氧树脂，复合物的介电性能、导热性能和机械性能均有比较大的增加。
表1 复合物的介电、导热和机械性能
Figure 633114DEST_PATH_IMAGE002
图2为本发明所用的高强度空心陶瓷球。
图3为本发明所用的空心陶瓷球横截面电子显微镜图。
图6为本发明制备的梯度复合物部件的一个示意图。
图7为本发明制备的梯度复合物部件的另一个实例示意图。
以上所述，仅为本发明的较佳实施例，并不用以限制本发明，各个实施例均采用递进的方式描述，各个实施例之间相同相似的部分互相参见即可，每个实施例重点说明的都是与其他实施例的不同之处。凡是依据本发明的技术实质对以上实施例所做的任何细微修改，等同替换和改进，均应包含在本发明技术方案的保护范围之内。

Claims (5)

1.一种含有空心陶瓷球复合物的耐冲击梯度复合物部件的3D打印方法，其特征在于，包括如下步骤：
1)设计部件的尺寸和形状以及内部的层状结构；
2)提供两种原材料，一种是金属粉末，另一种是空心陶瓷球；
3)根据设计提供一定厚度的金属粉末，然后用热源将粉末熔融和固化，形成金属层，根据设计重复打印金属层直到达到设计的金属层厚度；
4)在金属层表面提供一层空心陶瓷球，提供金属粉末直到所有球之间的空隙被填满，然后用热源将粉末熔融和固化，形成金属-陶瓷球复合物层，重复打印复合物层直到达到设计的厚度；
5)重复步骤3)和4)形成耐冲击梯度复合物部件；
6）在真空下高温处理进一步使凝聚固化并去除产物中的应力；
所述空心陶瓷球的直径为50微米-5毫米，空心陶瓷球壁厚同球半径的比例为1/3-2/3。
2.根据权利要求1所述的方法，其特征在于，所述空心陶瓷球的破碎率在35MPa下小于5%，在60MPa下小于5%，在压强高于86MPa时小于5%。
3.根据权利要求1或2所述的方法，其特征在于，所述空心陶瓷球的材料包括但不限于：玻璃，SiO2，刚玉，莫来石。
4.根据权利要求1所述的方法，其特征在于，所述金属粉末包括但不限于铝粉和钛粉。
5.如权利要求1-4任一项所述的方法制备得到的含有空心陶瓷球复合物的耐冲击梯度复合物部件。
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